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Ch15 Sample Exercise 001
Ch15 Sample Exercise 001
Solution
Analyze: We are given three equations and are asked to write an equilibrium-constant expression for each.
Plan: Using the law of mass action, we write each expression as a quotient having the product concentration
terms in the numerator and the reactant concentration terms in the denominator. Each concentration term is
raised to the power of its coefficient in the balanced chemical equation.
Practice Exercise
Practice Exercise
Solution
Analyze: We are first asked to judge the relative magnitudes of three equilibrium constants and then to
calculate them.
Plan: (a) The more product that is present at equilibrium, relative to the reactant, the greater the equilibrium
constant. (b) The equilibrium constant is given by the concentrations of products over reactants.
Using this information, write the equilibrium constant expression and calculate the equilibrium constant for
the following reaction:
Solution
Analyze: We are asked to write the equilibrium-constant expression for a reaction and to determine the
value of Kc given the chemical equation and equilibrium constant for the reverse reaction.
Plan: The equilibrium-constant expression is a quotient of products over reactants, each raised to a power
equal to its coefficient in the balanced equation. The value of the equilibrium constant is the reciprocal of
that for the reverse reaction.
Solve:
Writing products over reactants, we have
Both the equilibrium-constant expression and the
numerical value of the equilibrium constant are the
reciprocals of those for the formation of NO from N2
and O2:
Comment: Regardless of the way we express the equilibrium among NO, N2, and O2, at 25 C it lies on the side
that favors N2 and O2. Thus, the equilibrium mixture will contain mostly N2 and O2, with very little NO present.
Chemistry: The Central Science, Eleventh Edition
By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy
With contributions from Patrick Woodward
Solution
Analyze: We are given two equilibrium equations and the corresponding equilibrium constants and are
asked to determine the equilibrium constant for a third equation, which is related to the first two.
Plan: We cannot simply add the first two equations to get the third. Instead, we need to determine how to
manipulate the equations to come up with the steps that will add to give us the desired equation.
Solve: If we multiply the first equation
by 2 and make the corresponding
change to its equilibrium constant
(raising to the power 2), we get
Practice Exercise
Solution
Analyze: We are given two chemical equations, both for heterogeneous equilibria, and asked to write the
corresponding equilibrium-constant expressions.
Plan: We use the law of mass action, remembering to omit any pure solids, pure liquids, and solvents from
the expressions.
Solve:
(a) The equilibrium-constant expression is
Because H2O appears in the reaction as a pure liquid, its concentration does not appear in the equilibriumconstant expression.
(b) The equilibrium-constant expression is
Because SnO2 and Sn are both pure solids, their concentrations do not appear in the equilibrium-constant
expression.
Chemistry: The Central Science, Eleventh Edition
By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy
With contributions from Patrick Woodward
Solution
Analyze: We are asked which of several combinations of species can establish an equilibrium between
calcium carbonate and its decomposition products, calcium oxide and carbon dioxide.
Plan: For equilibrium to be achieved, it must be possible for both the forward process and the reverse
process to occur. For the forward process to occur, there must be some calcium carbonate present. For the
reverse process to occur, there must be both calcium oxide and carbon dioxide. In both cases, either the
necessary compounds may be present initially, or they may be formed by reaction of the other species.
Solve: Equilibrium can be reached in all cases except (c) as long as sufficient quantities
of solids are present. (a) CaCO3 simply decomposes, forming CaO(s) and CO2(g) until the equilibrium
pressure of CO2 is attained. There must be enough CaCO3, however, to allow the CO2 pressure to reach
equilibrium. (b) CO2 continues to combine with CaO until the partial pressure of the CO2 decreases to the
equilibrium value. (c) There is no CaO present, so equilibrium cannot be attained because there is no way
the CO2 pressure can decrease to its equilibrium value (which would require some of the CO2 to react with
CaO). (d) The situation is essentially the same as in (a): CaCO3 decomposes until equilibrium is attained.
The presence of CaO initially makes no difference.
Solution
Analyze: We are given a balanced equation and equilibrium partial pressures and are asked to calculate the
value of the equilibrium constant.
Plan: Using the balanced equation, we write the equilibrium-constant expression. We then substitute the
equilibrium partial pressures into the expression and solve for Kp.
Solve:
Practice Exercise
An aqueous solution of acetic acid is found to have the following equilibrium concentrations at 25 C:
[HC2H3O2] = 1.65 102 M; [H+] = 5.44 104 M; and [C2H3O2] = 5.44 104 M. Calculate the equilibrium
constant Kc for the ionization of acetic acid at 25 C. The reaction is
Answer: 1.79 105
Solution
Analyze: We are given the initial concentrations of H2 and l2 and the equilibrium concentration of HI. We
are asked to calculate the equilibrium constant Kc for
Plan: We construct a table to find equilibrium concentrations of all species and then use the equilibrium
concentrations to calculate the equilibrium constant.
Solve: First, we tabulate the initial and
equilibrium concentrations of as many
species as we can. We also provide
space in our table for listing the
changes in concentrations. As shown, it
is convenient to use the chemical
equation as the heading for the table.
Second, we calculate the change in
concentration of HI, which is the
difference between the equilibrium
values and the initial values:
Notice that the entries for the changes are negative when a reactant is consumed and positive when a product
is formed.
Chemistry: The Central Science, Eleventh Edition
By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy
With contributions from Patrick Woodward
Because Qc < Kc, the concentration of HI must increase and the concentrations of H2 and I2 must decrease to
reach equilibrium; the reaction will proceed from left to right as it moves toward equilibrium.
Chemistry: The Central Science, Eleventh Edition
By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy
With contributions from Patrick Woodward
Solution
Analyze: We are given an equilibrium constant, Kp, and the equilibrium partial pressures of two of the three
substances in the equation (N2 and H2), and we are asked to calculate the equilibrium partial pressure for the
third substance (NH3).
Plan: We can set Kp equal to the equilibrium-constant expression and substitute in the partial pressures that
we know. Then we can solve for the only unknown in the equation.
Solve: We tabulate the equilibrium
pressures as follows:
In which direction will the equilibrium shift when (a) N2O4 is added, (b) NO2 is removed, (c) the total
pressure is increased by addition of N2(g), (d) the volume is increased, (e) the temperature is decreased?
Solution
Analyze: We are given a series of changes to be made to a system at equilibrium and are asked to predict
what effect each change will have on the position of the equilibrium.
Plan: Le Chteliers principle can be used to determine the effects of each of these changes.
Solve:
(a) The system will adjust to decrease the concentration of the added N2O4, so the equilibrium shifts to the
right, in the direction of products.
(b) The system will adjust to the removal of NO2 by shifting to the side that produces more NO2; thus, the
equilibrium shifts to the right.
(c) Adding N2 will increase the total pressure of the system, but N2 is not involved in the reaction. The
partial pressures of NO2 and N2O4 are therefore unchanged, and there is no shift in the position of the
equilibrium.
(d) If the volume is increased, the system will shift in the direction that occupies a larger volume (more gas
molecules); thus, the equilibrium shifts to the right. (This is the opposite of the effect observed in Figure
15.13, where the volume was decreased.)
(e) The reaction is endothermic, so we can imagine heat as a reagent on the reactant side of the equation.
Decreasing the temperature will shift the equilibrium in the direction that produces heat, so the equilibrium
shifts to the left, toward the formation of more N2O4. Note that only this last change also affects the value of
the equilibrium constant, K.
Chemistry: The Central Science, Eleventh Edition
By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy
With contributions from Patrick Woodward
in which direction will the equilibrium shift when (a) Cl2(g) is removed, (b) the temperature is decreased, (c)
the volume of the reaction system is increased, (d) PCl3(g) is added?
Answer: (a) right, (b) left, (c) right, (d) left
(b) Determine how the equilibrium constant for this reaction should change with temperature.
Solution
Analyze: We are asked to determine the standard enthalpy change of a reaction and how the equilibrium
constant for the reaction varies with temperature.
Plan: (a) We can use standard enthalpies of formation to calculate H for the reaction. (b) We can then
use Le Chteliers principle to determine what effect temperature will have on the equilibrium constant.
Solve:
(a) Recall that the standard enthalpy change for a reaction is given by the sum of the standard molar
enthalpies of formation of the products, each multiplied by its coefficient in the balanced chemical equation,
less the same quantities for the reactants. At 25 C, Hf for NH3(g) is 46.19 kJ/mol. The Hf values for
H2(g) and N2(g) are zero by definition because the enthalpies of formation of the elements in their normal
states at 25 C are defined as zero (Section 5.7). Because 2 mol of NH3 is formed, the total enthalpy change
is
(b) Because the reaction in the forward direction is exothermic, we can consider heat a product of the
reaction. An increase in temperature causes the reaction to shift in the direction of less NH3 and more N2
and H2. This effect is seen in the values for Kp presented in Table 15.2. Notice that Kp changes markedly
with changes in temperature and that it is larger at lower temperatures.
Chemistry: The Central Science, Eleventh Edition
By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy
With contributions from Patrick Woodward
Use this result to determine how the equilibrium constant for the reaction should change with temperature.
Answer: H = 508.3 kJ; the equilibrium constant will increase with increasing temperature
There are no entries in the table under C(s) because the reactant, being a solid, does not appear in the
equilibrium-constant expression. Substituting the equilibrium partial pressures of the other species into the
equilibrium-constant expression for the reaction gives
(b) Part (a) shows that x = 6.14 atm of H2O must react for the system to achieve
equilibrium. We can use the ideal-gas equation to convert this partial pressure into a
mole amount.
Thus, 0.0697 mol of H2O and the same amount of C must react to achieve equilibrium. As a result, there
must be at least 0.0697 mol of C (0.836 g C) present among the reactants at the start of the reaction.
(c) The total pressure in the vessel at equilibrium is simply the sum of the equilibrium partial pressures:
(d) In discussing Le Chteliers principle, we saw that endothermic reactions exhibit an increase in Kp with
increasing temperature. Because the equilibrium constant for this reaction increases as temperature
increases, the reaction must be endothermic. From the enthalpies of formation given in Appendix C, we can
verify our prediction by calculating the enthalpy change for the reaction,
H = Hf(CO) + Hf(H2) H (C) Hf(H2O) = +131.3 kJ. The positive sign for H indicates that
the reaction is endothermic.
(e) According to Le Chteliers principle, a decrease in the pressure causes a gaseous equilibrium to shift
toward the side of the equation with the greater number of moles of gas. In this case there are two moles of
gas on the product side and only one on the reactant side. Therefore, the pressure should be reduced to
maximize the yield of the CO and H2.
Chemistry: The Central Science, Eleventh Edition
By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy
With contributions from Patrick Woodward